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Publication numberUS3242150 A
Publication typeGrant
Publication dateMar 22, 1966
Filing dateMar 31, 1960
Priority dateMar 31, 1960
Also published asDE1520461B
Publication numberUS 3242150 A, US 3242150A, US-A-3242150, US3242150 A, US3242150A
InventorsJack S Scoggin
Original AssigneePhillips Petroleum Co
Export CitationBiBTeX, EndNote, RefMan
External Links: USPTO, USPTO Assignment, Espacenet
Method and apparatus for the recovery of solid olefin polymer from a continuous path reaction zone
US 3242150 A
Abstract  available in
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Claims  available in
Description  (OCR text may contain errors)

March 22, 1966 J. 5. SCOGGIN 3,242,150

METHOD AND APPARATUS FOR THE RECOVERY OF SOLID OLEFIN POLYMER FROM A CONTINUOUS PATH REACTION ZONE Filed March 51, 1960 HEAT EXCHANGE 2 FLUID --1 H}' 12 1| L REACTION $51: SAMPLE 2 4--- 1 l -J T l i CATALYST I 5 i I DILUENT 4 7 1 I I 3 "1| r 1 l ETHYLENE: -l g L. I I

l .L |3 lcidi I l i I I HEAT EXCHANGE F I 1 I FLUID L L 1 I i I i |O I I a 9 {n- 'I '5 1L0 E **"""-T-**.6 a l 22 O a 1:}--- I 2 2s 25 30X? 20 l L f1 29- I ,JDRYER J "1 DRY POLYMER INVENTOR. J.S. scoscm I I ATTONE s United States Patent 3 242 150 METHOD AND APPAR ATE JS FOR THE RECGVERY 0F SQUID @LEFEN PQLYMER FROM A CQNTIN- UfllUtl PATH REACTI'UN ZQNE Jack 5. Seoggin, llartlesville, Okla, assignor to Phillips Petroleum (Iompany, a corpcratien of Delaware Filed l /iar. 31, 1960, No. 19,007 21 Claims. (Cl. 260--S8.Z)

This invention relates to the recovery of olefin polymers from hydrocarbon slurries thereof. In one aspect, the invention relates to improved methods and apparatus for recovering particulate olefin polymers from continuous path reactors.

One method of carrying out particle form polymerization of ethylene and mixtures of ethylene with other unsaturated hydrocarbons is described in the copending application of Donald D. Norwood, Serial No. 819,391, filed June 10, 1959, now abandoned. In this copending application a method and apparatus is described for reducing the fouling of reaction surfaces by carrying out the polymerization reaction in a tubular closed loop reaction zone with smooth surfaces. The catalyst, liquid diluent and hydrocarbon reactants are continuously moved through the reaction zone at a velocity in the highly turbulent flow range thereby producing a solid particle form polymer product which is then withdrawn from the reaction zone. Means are disclosed therein for converting the rotational energy of the propellers into flow energy with a minimum loss of energy.

This invention represents an improvement on the aforementioned copending application of Norwood. A major consideration in the etfiicent operation of a continuous path loop reactor is the removal of the product from the reactor. Prior methods of removal of the product require the simultaneous removal of large quantities of diluent and reactants which then need to be separated from the product and processed for return to the reactor.

It is an object of this invention to provide an improved method and apparatus for recovering high molecular weight, solid particulate form polymers from a hydrocarbon slurry thereof.

It is another object of this invention to provide an improved method and apparatus for recovering high molecular weight, solid particulate form polymers from a hydrocarbon slurry thereof from a continuous path loop reactor.

It is another object of this invention to provide an improved method and apparatus for curtailing further polymerization of the reactants removed from the reactor with the polymer product.

These and other objects of the invention will become more readily apparent from the following detailed description and discussion.

The foregoing objects are realized broadly by carrying out the polymerization reaction in a tubular closed loop reaction zone with smooth surfaces; liquid diluent and hydrocarbon reactants being continuously moved through said zone at a velocity in the highly turbulent flow range; the produced polymer being permitted to gravitate from said reaction zone into a receiving zone thereby collecting a fraction concentrated in particulate solid polymer product and solid particle form product being withdrawn from said receiving zone.

In one aspect of the invention a diluent is introduced into the receiving zone to maintain the temperature of the recovered polymer product below its softening point thereby reducing the possibility of fusion of the polymer and thereby eliminating plugging and fouling of the receiving zone.

In another aspect of the invention the velocity of the reactants within the loop reaction zone is varied proportionally to the quantity of particulate solids in the receiving zone.

3,242,15 Patented Mar. 22, I966 It is disclosed in Hogan er al., US. Patent 2,825,721,

that polymers and copolymers can be produced by contacting one or more olefins with a catalyst comprising as an essential ingredient chromium oxide, preferably including a substantial amount of hexavalent chromium. The chromium oxide is associated with at least one other oxide particularly selected from the group consisting of silica, alumina, zirconia and thoria. The olefin feed used for the polymerization is at least one olefin selected from 1-olefins having .a maximum of 8 carbon atoms per molecule and no branching nearer the double bond than the 4-position. Examples of olefins which can be polymerized by the described method include ethylene, propylene, 1-butene, l-pentene and 1,3-butadiene. Copolymers, such as ethylene-propylene copolymers and ethylene-butadicne copolymers, can also be prepared by utilizing the chromium oxide containing catalyst. The olefins are polymerized in the presence of a hydrocarbon diluent, for example, an acyclic, alicyclic or aromatic compound which is inert.

Recently it has been discovered that there is a critical polymerization temperature range within the broad range disclosed by Hogan et al. in which it is possible to produce increased yields of high molecular Weight polymers of ethylene which are insoluble in the hydrocarbon diluent. This polymer is formed in association with the polymerization catalyst and is suspended in the liquid diluent in solid particle form. The preparation of insoluble particle form polymer is disclosed in the copending application of Leatherrnan et al., Serial No. 590,567, filed June 11, 1956. In the following discussion the term particle form polymer will be employed to designate the insoluble polymers of ethylene formed in accordance with the Leatherman et al. application.

Particle form polymer can be prepared from ethylene and from mixtures of ethylene with other unsaturated hydrocarbons, for example, mixtures of ethylene with minor amounts of higher l-olefins, such as propylene, l-bntene, l-pentane, l-hexene, and the like. Examples of coinonomers which can be used with ethylene include l-olelin s having no branching nearer the double bond than the 4aposition and conjugated and non-conjugated diolefins. The polymerization reaction is carried out in the presence of a liquid hydrocarbon diluent which is inert in the polymerization reaction and in which the majority of the polymer is insoluble under reaction conditions. Suitable diluents include panafiins such as those having from 3 to 12 and preferably 3 to 8 carbon atoms per molecule, for example, n-butane, napentane, isopentane, n-hex'ane, n-decane, etc., saturated cyclic hydrocanbons such as cyclohex'ane, :cyclopentane and methylcyclolpentane, methylcyclohexane, etc. The polymerization reaction temperature will vary depending on the particular liquid diluent which is employed and on the olefin reactants. Usually, however, polymerization is carried out at 260 F. and below, preferably between about 225 F. and about F. The olefin reactants are contacted in the polymerization zone with a suspension of subdivided chromium oxide catalyst in the liquid hydrocarbon diluent under the aforementioned temperatures and under pressures suitable to maintain the diluent in the liquid phase. Concentration of the catalyst in the reaction zone can vary widely; however, generally it will be in the range of 0.001 to 5 percent by weight based on the liquid hydrocanbon diluent. Fora more detailed description of the polymerization process including reaction conditions, catalyst, etc., reference can be had to the lcopendin g application of Le-atherman et al., Serial No. 590,567, filed June I l, 1956, now abandoned.

By the method and apparatus of this invention the polymer product may be continuously recovered from the loop reactor with a minimum of accompanying liquid diluent 1' and hydrocarbon reactants. This minimizes the need for the recycling of olefin and the recycling of diluent from the product recovery zone to the reaction zone. Further, the use of the receiving zone results in an increase in polymer concentration prior to the polymer product recovery zone thereby decreasing the load on said zone. Further, by permitting the reactants to remain in the reaction zone for a longer period of time prior to withdrawal the olefin conversion is increased considerably, thereby resulting in an improved economic climate. Another advantage to this system is that less new diluent is introduced to the reactor thereby decreasing the possibility of the introduction of catalyst poisons into the reactor system. Catalyst productivity is also generally improved with a consequent lower ash content in the product.

By the method of this invention an appendage is attached to the loop reactor in such a manner that the flowing reactants and diluent will continuously pass the entrance to said appendage, herein referred to as a receiving zone, in such a manner that the heavier particles will continuously gravitate from the flowing reactants and diluent into the receiving zone 'While the lighter diluent and reactants Will continually flow across the entrance to said receiving zone thereby resulting in the collection within said receiving zone of a fraction concentrated in particulate polymer solids. This receiving zone may be of any type so long as the entrance thereto is large enough to prevent bridging of the polymer and not so large as to result in an unduly large amount of diluent and reactants being entrapped in the receiving zone. It has been found that the polymer production rate is a function of the settling area, i.e., the diameter of the entrance to the receiving zone. The required length of the receiving zone is also a function of the velocity as well as the inventory of polymer within the receiving zone. For instance, when using a 10 inch I.D. reactor, a 1% inch receiving zone, and a reactor velocity of approximately 8 ft./sec., the turbulent zone extends approximately 5 /2 receiving zone diameters into said receiving zone so the length must extend past this point -to provide .a zone of relative quiet. When the polymer solids concentration is 20-25 percent within the reactor using a 10-14 ft./se'c. linear velocity, the polymer will build up within the zone at an approximate rate of 1 to 2 'ft./minute. As illustrated by the attached drawing the receiving zone may consist of a simple tube appended to the lower side of the reaction zone. In the case of a 10 inch I.D. loop reactor the entrance to the receiving zone may be approximately 1 and 4 inch in diameter. Preferably, the length of the zone will be at least three times the diameter of the receiving zone, more preferably 4 to 40 times. The entrance diameter will be a function of the desired production rate. In general, it is more advantageous to have a multiple number of small diameter receiving zones than a single large diameter unit to increase the flexibility of control over production rate. It would be within the scope of the invention to use other conventional types of settling tanks such as .a liquid-solid cyclone, centriclone, centrifuge, etc., or a series of said settling tanks.

In the normal operation of the receiving zone the particles collected therein are in the form of particulate solids. At the lower extremity of the receiving zone may be located a valve which periodically opens and closes completely so as to permit the removal of polymer product. In view of the fact that the loop reactor is operated under superatmospheric pressure and the valve opens into acondu-it of approximately atmospheric pressure the hydrocarbon diluent and reactants will be rapidly evaporated and the gases expanded so as to propel the polymer product through the conduit to the product polymer recovery zone. Two valves may be incorporated within the receiving zone permitting the entrapment of a portion of the settled polymer product. Periodically the bottom valve would be closed and the upper valve would open to permit the introduction of polymer product into the lock; then of said receiving zone.

the top valve would close and the bottom valve would open to prevent the escape of the polymer with the small amount of accompanying diluent and reactant. The valve, or the series of valves, are normally fully opened or fully closed and may be operated on a time cycle.

As discussed above the polymer product accumulating in the receiving zone is normally a solid particulate polymer which is easily removed from the receiving zone by the method or methods described above. However, if the timing or the removal of the polymer from the receiving zone is not carefully controlled the reactants which accompany the polymer into the receiving zone have an ideal environment for further polymerization. In view of the fact that the olefin polymerization reaction is normally exothermic the evolved heat results in the fusion of the accumulated polymer product thereby resulting in the agglomeration of said product into a mass which may be difficult to remove from the receiving zone. In one aspect of this invention the heat evolved in the receiving zone is continuously removed so as to prevent the elevation of temperature within the receiving zone to above the fusion point of the polymer product. Any conventional method of removing heat may be utilized such as a heat exchange system, direct or indirect. The fusion problem may also be alleviated by removing the reactants from the receiving zone before they have an opportunity to further polymerize. One suitable method is to inject a diluent into the bottom of the receiving zone thereby cooling said receiving zone. The diluent may range in temperature from ambient temperature to slightly below the reaction zone temperature; for polyethylene, this would be ambient temperature to about 225 F.; more preferably, about 70 F. to about 200 F. If the velocity of the diluent entering the receiving zone from near the bottom is in excess of the velocity of the reactants entering the receiving zone from the loop reaction the reactants will be elutriated back into the loop reactor. It is, of course, essential that the volume of diluent not be excessive and that the velocity be such that the reactants will be removed from the receiving zone but that the particulate solids will be permitted to settle therein. This introduction of a diluent, such as the diluent used in the loop reactor, into the bottom of the receiving zone may be varied in response to a signal from a thermocouple Within the receiving zone which measures the temperature As the temperature in the receiving zone increases the amount of diluent injected into said receiving zone is increased and vice versa. Any type of conventional temperaure control system may be used such as a Foxboro model 40 recorder controller as described in Foxboro bulletin 5 A10 Z (1955).

In another aspect of this invention this secondary polymerization reaction is controlled by adjusting the residence time of the polymer product within the receiving zone. This may be accomplished by increasing the withdrawal rate from the polymerization zone. However, this is ordinarily undesirable because it also means the withdrawal of an increased amount of reactants and diluent from the reaction zone thereby negating some of the advantages of the receiving zone.

A preferable method of adjusting the residence time within the receiving zone is by varying the velocity of the reactants and diluent within the reactor zone in direct proportion to the volume of solids within the receiving zone. As the velocity of the diluent and reactants is increased within theloop reactor the amount of particulate solids gravitating from said reaction zone into said receiving zone is thereby decreased, and vice versa. Therefore, any conventional measuring device may be used to determine the volume of solids within the receiving zone which will transmit a signal to the propelling means to adjust the velocity. When using a constant volume re ceiving zone a simple device for measuring the depth of solids within the receiving zone may be used, such as a gamma ray density gauge or by focusing a light beam through the reactor at the maximum and minimum desired levels. Either means will indicate when the solids depth level is outside the desired range. When using a variable speed motor with propellers to propel the liquid an increase in the depth of the solids within the receiving zone will result in a signal transmission to the variable speed motor to increase the motor speed thereby reducing the depth of settled material in the receiving zone. When the solids depth level reaches the minimum desired point the converse will occur.

The location of the receiving zone with respect to the loop reactor system is not particularly important so long as the particulate solids produced may gravitate into the receiving zone. In the preferred method of operation the receiving zone will be located on the under side of one of the horizontal legs of the reactor so that the direction of flow within the reactor will be perpendicular to the receiving zone.

It is surprising that the utilization of the receiving zone of this invention in conjunction with the loop reaction system will result in the concentration of polymer from the 1820 percent found within the reactor to approximately 55 percent within receiving zone. These concentrations will vary, of course, with the reactants and the reaction conditions within the reaction zone. It is further surprising that by the utilization of this invention the conversion of the reactants is increased. For example, it has been found that it is possible to increase the ethylene conversion from 50 to 70 percent to approximately 85 to 95 percent. When forming a copolymer of ethylene and l-butene it has been found that the increase of hutene conversion is from 25 percent to approximately 50 percent. Conversion is determined by dividing the amount of product by the amountof monomer introduced into the loop reactor.

The invention is best described by reference to the ac companying drawing.

Reactor 1, which is oblong in shape, is made of flanged straight pipe sections and Us joined together to provide a continuous flow path which is substantially free from obstructions. The reactor is jacketed by section i which forms an annular space '16 with the reactor 1. By means of inlet 13 and outlet 14 a heat exchange fluid is permitted to flow through annular space 19 to control the temperature of the reactor. Conduit 2 is provided for the introduction of catalyst and diluent into the reactor and conduit 3 is provided for the introduction of ethylene into the reactor. Conduit 11 and valve 12 are provided for the periodic removal of a reaction sample to ascertain the conditions within the reactor. Thermocouples can be provided for sensing the temperature in the reactor. Prorvision can be made to transmit the measurement of the reactor temperature to a temperature recorder controller (not shown) which can be utilized to control the reactor temperature. Various control methods can be used including control of the heat exchange fluid to jacket 9, control of the quantity and/ or temperature of reactants entering the reactor, control of the amount of catalyst entering the reactor, etc. Vertically disposed drive shaft '4 connects to propellers 5 and 6. Suitable means can be provided outside the reactor, such as variable speed motor 8, for actuating the drive shaft 4 and propellers 5 and 6. Considerable agitation is produced by propellers 5 and 6 and this is converted in part to how energy by providing straightening vanes 7, formed by metal plates projecting perpendicularly from the inner wall of the reactor and positioned adjacent to propellers 5 and 6. Any suitable means may be used to convert rotational energy to flow energy.

In the apparatus shown the vertical leg in which the propellers are positioned is of substantially the same cross section as the remainder of the reactor, however, if desired, the vertical leg may be of larger or smaller diameter than the remainder of the reactor. The various parts which make up the reactor are constructed to provide a smooth, continuous, inner surface presenting a minimum of obstruction to flow. The only obstructions of any consequence in the reactor are the propellers 5 and 6 and straightening vanes 7. The reactor may be made up of flanged sections or partially or completely welded.

The receiving zone, as shown in the drawing, consists of a pipe welded directly onto the reactor outside Wall and extending through the heat exchange jacket thereby establishing open communication with the reactor at 15. This section terminates in a 'fiange 16 through which the receiving zone '17 protrudes from the reactor to some distance below the reactor thereby forming a receiving chamber or zone. In the case of a gallon reactor having a 10 inch internal diameter, this receiving zone can be a 1% inch LD. pipe some 43 inches in length welded to said reactor. The size of the opening the size of the pipe and the capacity of the receiving zone will be varied within considerable limits to fit the conditions of operation. At the terminus of receiving zone 17 is located a valve 18 which is periodically in the completely open or the completely closed position. The valve port may be a 'slot, for instance, inch by 1% inch or a simple round opening, such as inch in diameter. A suitable rnethod of activating the valve is by the use of a 5% inch stroke Rivet-t air cylinder. From the valve 18 the product and the diluent and reactants are transported by the expanding gases via conduit '19 to the product recovery zone.

Within the receiving zone 17 the temperature is sensed by a thermocouple 23 which transmits a signal to temperature recorder controller 22 which activates motor valve 2 1 in conduit 20 to permit the introduction of diluent into receiving zone 17 thereby cooling the contents thereof and, if desired, elutriating the reactants back into the reactor '1.

By means of solids depth level sensing means 24 and 25, which can be photoelectric type devices or gamma ray density gauges, etc:, a signal is transmitted to level controller 26 when the depth of solids is outside the range desired as predetermined by the arrangement of sensing means 24 and 25. This signal is then transmitted to the variable speed motor 8 for propelling the propellers 5 and 6 thereby increasing or decreasing the velocity of fluid within the reactor. When the level within the receiving zone 17 increases to above a predetermined level, a signal is transmitted to variable speed motor 8 so as to increase the rotational energy imparted to the propellers 5 and 6 thereby increasing the velocity of the fluid within the reactor, and vice versa. A safety valve may be incorporated in receiving zone 17 upstream of valve 18 with said safety valve being normally open so that in the result of a failure of valve 1 8 to close properly the safety valve will be actuated to close so as to prevent the loss of reactants and diluent.

The expanding gases resulting from the decrease in pressure from superatmospheric pressure to substantially atmospheric pressure in conduit-19 transport the reactants and diluent and product to the product recovery zone. This product recovery zone may include a dryer which may be a flash dryer to remove primary gases or a fluidized bed dryer, etc. For instance, when a copolymer of ethylene and l-butene is being produced by the use of a pentane diluent with a chromium oxide catalyst the contents of line 19 will comprise polymer product, gaseous pentane, and gaseous ethylene and labutene. The catalyst will be intimately associated with the polymer and will not ordinarily be separated therefrom. There will be a minimum amount of liquid at these essentially atmospheric conditions. From dryer 27 dry polymer will be removed through conduit 28 for packaging or further processing. Conduit 29 will transport the removed gases which will contain polymer fines which may be removed in a filter such as bag-filter 30. These polymer fines may then be further processed, returned to the dryer or discarded through conduit 45. The gases passing through the filter will be transported through conduit 40 into condenser 41 which will condense at least part of the gaseous components. The condensate will be removed through conduit 43 or returned to the reactor 9 or for further processing. The gases will be transported through conduit 42 to a flare for burning or returned to the reactor 9.

While the drawings have illustrated propeller means for imparting how to the reactor contents it is within the scope of the invention to provide other types of motive power. For example, the propellers can be replaced by a pump of the impeller type. With a suitably designed pump, namely one which provides a maximum of flow energy, it is possible to reduce or entirely eliminate the use of straightening vanes in the reactor. Any conventional driver including a motor, turbine, etc., can be utilized for actuating the propellers, pump or other motive means provided for moving the reactor contents.

The following data are presented to illustrate the invention.

Monomers of ethylene and butene-l were introduced into a loop reactor of the type shown in the drawing. The loop reactor had a uniform 10 inch internal diameter, except the section housing the impeller which had a 12 inch ID. The receiving zone which was appended to the lower portion of the lower horizontal leg of the reactor comprised a 1% inch l.D. pipe some 43 inches in length which was welded directly to the reactor and in open communication with the interior thereof. Two runs were made to compare the efiiciency of the loop reactor Without a settling leg or receiving zone using valve 12 and conduit 1 1 to continuously withdraw polymer and with a receiving zone 17. The following data compare the operating conditions and the results of those two runs and are presented in illustration of the invention:

EXAMPLE With Without Receiving Receiving Zone Zone Loop Reactor Conditions:

Capacity, gal 95 95 Pressure, p.s.i.g 450 450 Reaction Temperature (44) 205 205 Coolant Temperature, F.:

In (13) 190 177 Out (14) 194 184 Loop Reactor Influent, lbs./hr.:

lo (3) 21 39 0. 5 0.8 Pcntanc (2) 15. 75 99. Chromium oxide catalyst (2) 0.008 0. 008

Dryer Influent (19), lbs./hr.:

Ethylene 1. 25 19. 1 Butane-1 0. 25 0. 7 Pentane..- 15. 75 99. 0 Cataly 0. 008 0.0 Polymer 20. 0 20. 0

Etllcicncy:

Percent Solids in dryer inilucnt (19). 53. 7 14. 4 Ethylene Conversion, pcrccnt 94 51 Butane-1 Conversion, percent; 50 25 Dryer (27) Duty, Btu/lb. of polymer. 88 555 Polymer Properties:

High Load Melt Index 1 5. 28 1.99 Density, gmsJcc. 0. 937 0. 951 Ash, wt. percent 0. 04 0. 04

1 The method of ASTM D-1238-52T was used exccpt that the polymer sample is allowed to extrude from the test apparatus for 9 minutes at which time the cxtrudate is cut oil with a spatula. The extrudate is cut off again at the end of 11 minutes. The 9 to 11 minute cut is weighed. This weight is multiplied by and reported as the melt index value. This test is run under high load conditions (21,600 girls).

1 Density as used herein is determined by compression molding a slab of the polymer, cooling said molding at a temperature reduction rate of to F. per minute to room temperature, cutting a pea-sized specimen therefrom, and placing said specimen in a -rnl. glass-stoppercd graduate. Carbon tetrachloride and methyl cyclohexanc are added to the graduate from burcttcs in proportion such that the specimen is suspended in the solution. During the addition of the liquids the graduate is shaken to secure thorough mixing. When the mixture just suspends the specimen, a portion of the liquid is transl'crrcd to a small test tube and placed on the platform at a Wcstphal balance and the glass bob lowered therein. With the temperature shown by the thermometer in tho bob in the range 73 to 78 F., the balance is adjusted until the pointer is at zero The value shown on the scale is taken as the specific gravity.

As can be seen from the above tabulation the effi-ciency of the loop reactor is greatly improved by the use of the settling leg of this invention.

While certain examples, structures, composition and process steps have been described for purposes of illustration, the invention is not limited to these. Variation and modification within the scope of the disclosure and the claims can readily be effected by those skilled in the ant.

What I claim is:

l. In a process for the polymerization of a l-olelin by contacting said l-olefin with a catalyst and a diluent within a smooth continuous path reaction zone at a temperature and pressure such that substantially all the diluent is in the liquid phase and the polymer produced is insoluble in said diluent and is in the form of solid particulate polymer having a density greater than said diluent, said polymer, catalyst, l-olefin and diluent being continuously moved through said continuous path reaction zone at a velocity in the highly turbulent flow range, the improvement Which comprises removing said particulate solids from said zone by causing said particulate solids to gravitate from said reaction zone into a receiving zone thereby collecting a fraction concentrated in product polymer solids while substantially all the diluent, l-olefin and catalyst continue to flow across the entrance to the receiving zone and remain within said reaction zone and withdrawing said fraction from said receiving zone.

2. In a process for the polymerization of a l-olefin by contacting said l-olefin with a catalyst and a diluent within a smooth continuous path reaction zone at a temperature and pressure such that substantially all the diluent is in the liquid phase and the polymer produced is insoluble and suspended in said diluent and is in the form of solid particulate polymer having a density greater than said diluent, said polymer, catalyst, l-olefin and diluent being continuously moved through said continuous path reaction zone at a velocity in the highly turbulent flow range, the improvement which comprises removing said particulate solids from said zone by causing said particulate solids to continuously gravitate from said reaction zone into a receiving zone in open communication with said reaction zone thereby collecting, by settling, a fraction concentrated in product polymer While substantially all the diluent, l-olefin and catalyst continue to flow across the entrance to the receiving zone and remain within said reaction zone, introducing suiticient diluent into said receiving zone to maintain the temperature of said particulate polymer below the softening point of said polymer and withdrawing said product polymer fraction from said receiving zone.

3. The process of claim 2 wherein the volume of diluent introduced into said receiving zone is varied directly proportional to temperature changes within the receiving zone.

4. The process of claim 2 wherein the velocity of upwardly flowing diluent within the receiving zone is sufficient to elutriate at least part of the reactants back into the reaction zone but is not great enough to prevent the settling of the desired polymer product particles.

5. In a process for the polymerization of a l-olefin by contacting said l-olefin with a catalyst and a diluent within a smooth continuous path reaction zone at a temperature and pressure such that substantially all the diluent is in the liquid phase and the polymer produced is insoluble and suspended in said diluent and is in the form of solid particulate polymer having a density greater than said diluent, said polymer, catalyst, l-olefin and diluent being continuously moved through said continuous path reaction zone at a velocity in the highly turbulent flow range, the improvement which comprises removing said particulate solids from said zone by causing said particulate solids to continuously gravitate from saidreaction zone into a receiving zone in open communication with said reaction zone thereby collecting by settling a fraction concentrated in product polymer while substantially all the diluent, l-olefin and catalyst continue to flow across the entrance to the receiving zone and remain within said reaction zone, varying the flow rate of the reactants within said reaction zone directly proportional to the quantity of particulate solids contained in said receiving zone thereby maintaining a substantially constant residence time for polymer within said receiving zone and withdrawing said polymer product fraction from said receiving zone.

6. The method of claim wherein the flow rate is varied directly proportional to the depth of particulate solids within the receiving zone.

7. In a process for the polymerization of a l-olefin by contacting said l-olefln with a catalyst and a diluent within a smooth continuous path reaction zone in turbulent flow at a temperature and pressure such that substantially all the diluent is in the liquid phase and the polymer produced is insoluble and suspended in said diluent and is in the form of solid particulate polymer having a density greater than said diluent, said polymer, catalyst, l-olefin and diluent being continuously moved through said continuous path reaction zone at a velocity in the highly turbulent flow range, the improvement comprising removing said particulate solids from said zone by causing said particulate solids to continuously gravitate from said reaction zone into a receiving zone in open communication with said reaction zone thereby collecting by settling a fraction concentrated in product polymer while substantially all the diluent, l-olefin and catalyst continue to flow across the entrance to the receiving zone and remain within said reaction zone, introducing sufficient diluent into said receiving zone to maintain the temperature of said particulate solids below the softening point of said polymer, varying the flow rate of the re actants within said reaction zone directly proportional to the quantity of particulate solids contained in said receiving zone thereby maintaining a substantially constant residence time for polymer within said receiving zone and withdrawing said polymer product fraction from said receiving zone.

8. The process or" claim '7 wherein the velocity of the upwardly flowing diluent within the receiving zone is sufiicient to elutriate at least part of the reactants back into the reaction zone but is not great enough to prevent the settling of the desired polymer product polymers.

9. The process of claim 7 wherein the volume of diluent introduced into said receiving zone is varied directly proportional to temperature changes within the receiving zone and the flow rate within the reaction zone is varied directly proportional to the depth of particulate solids within said receiving zone.

10. In a process for the polymerization of ethylene by contacting said ethylene with a chromium oxide catalyst containing hexavalent chromium associated with an oxide selected from the group consisting of silica, alumina, thoria and zirconia in liquid normal pentane within a ver tically disposed smooth closed continuous path reaction zone of uniform cross-section and at a temperature in the range of between 225 F. and about 150 F. and a temperature such that substantially all the diluent is in the liquid phase whereby substantially all the polyethylene product is insoluble and suspended in said liquid normal pentane and is in the form of solid particles of polyethylene, said polyethylene, catalyst, normal pentane and ethylene being continuously moved through said continuous path reaction zone at a velocity in the highly turbulent range, the improvement which comprises removing said particulate solids from said zone by causing said partic ulate solids to gravitate from said reaction zone into a receiving zone in open communication with said reaction zone thereby collecting by settling a fraction concentrated in product polyethylene while substantially all the diluent, l-olefin and catalyst continue to flow across the entrance to the receiving zone and remain within said reaction zone,

introducing sufficient diluent into said receiving zone to maintain the temperature of said particulate polyethylene below the softening point of said polyethylene, varying the flow rate of the reactants within said reaction zone directly proportional to the quantity of particulate solids contained within said receiving zone thereby maintaining a substantially constant residence time for product within said receiving zone and withdrawing said polyethylene from said receiving zone.

11. The process of claim 10 wherein the volume of diluent introduced into said receiving zone is varied directly proportional to temperature changes within the said receiving zone and wherein said flow rate within the reaction zone is varied directly proportional to the depth of particulate solids within the receiving zone.

12. A process for the copolymerization of ethylene and l-butene by contacting ethylene and 'l-butene with a chromium oxide catalyst containing hexavalent chromium associated with an oxide selected from the group consisting of silica, alumina, thoria, and zirconia in liquid normal pentane within a vertically disposed smooth closed continuous path reaction zone of uniform cross-section and at a temperature in the range of between 225 F. and about F. and a temperature such that substantially all the diluent is in the liquid phase wherein substantially all of the particle form copolymer produced is insoluble and suspended in said liquid normal pentane and is in the form of solid particles of ethylene-l-butene copolymer, said copolymer, catalyst, normal pentane, ethylene and 1-butene being continuously moved through said continuous path reaction zone at a velocity in the highly turbulent flow range, the improvement which comprises removing said particulate solids from said zone by causing said particulate solids to gravitate from said reaction zone into a receiving zone in open communication with said receiving zone thereby collecting by settling the fraction concentrated in product copolymer while substantially all the diluent, l-olefin and catalyst continue to flow across the entrance to the receiving zone and re main within said reaction zone, introducing suflicient diluent into said receiving zone to maintain the temperature of said particulate copolymer below the softening point, varying the flow rate of the reactants within said reaction zone directly proportional to the quantity of particulate solids contained within said receiving zone thereby maintaining a substantially constant residence time for copolymer within said receiving zone and withdrawing said copolymer from said receiving zone.

13. The process of claim 12 wherein the volume of diluent introduced into said receiving zone is varied directly proportional to temperature changes within said receiving zone and wherein said flow rate within the reaction zone is varied directly proportional to the depth of particulate solids within the receiving zone.

14. In a process for the polymerization of a lolefin by contacting said l-olefin with a catalyst and a diluent within a smooth continuous path reaction zone in turbulent flow at a temperature and pressure such that substantially all the diluent is in the liquid. phase and the polymer produced is insoluble in said diluent and is in the form of solid particulate polymer having a density greater than said diluent, the improvement which comprises removing said particulate solids from said zone by causing said particulate solids to gravitate from said reaction zone into a receiving zone thereby collecting a fraction concentrated in product polymer solids while substantially all the diluent, l-olefin and catalyst continue to flow across the entrance to the receiving zone and remain within said reaction zone, reducing polymer agglorneration within said receiving zone by adjusting a process variable affecting secondary polymerization within said receiving zone, and withdrawing said fraction from said receiving zone.

15. Apparatus comprising in combination a tubular closed reactor with smooth bends, said reactor being substantially free from internal obstructions; means for introducing olefin reactant, polymerization catalyst and liquid hydrocarbon diluent into said reactor; means for continuously moving the contents of said reactor therethrough at a velocity in the turbulent flow range; receiving means comprising a vertically disposed appendage on a lower portion of a horizontal leg of said reactor establishing open communication with said reactor for continuously receiving particulate polymer solids gravitating from said reactor thereby producing a fraction concentrated in particulate solids; cooling means for maintaining the temperature of said particulate solids within said receiving means below the softening point of the polymer and means for withdrawing said fraction from said receiving means.

16. The apparatus of claim 15 wherein said cooling means comprises means for the injection of a diluent into said receiving means.

17. Apparatus comprising in combination a tubular closed reactor with smooth bends, said reactor being substantially free from internal obstructions; means for introducing olefin reactant, polymerization Catalyst and liquid hydrocarbon diluent into said reactor; means for continuously moving the contents of said reactor therethrough at a velocity in the turbulent flow range; receiving means comprising a vertically disposed appendage on a lower portion of a horizontal leg of said reactor establishing open communication with said reactor for continuously receiving particulate polymer solids gravitating from said reactor thereby producing a fraction concentrated in particulate solids; cooling means for maintaining the temperature of said particulate solids within said receiving means below the softening point of the polymer; temperature sensing means for determining the temperature within said receiving means; means connecting said temperature sensing means and said cooling means for varying the cooling in response to a variation in temperature within said receiving means and means for withdrawing said fraction from said receiving means.

18. Apparatus comprising in combination a tubular closed reactor with smooth bends, said reactor being substantially free from internal obstructions; means'for introducing olefin reactant, polymerization catalyst and liquid hydrocarbon diluent into said reactant; means for continuously moving the contents of said reactor therethrough at a velocity in the tubulent flow range; receiving means comprising a vertically disposed appendage on a horizontal leg of said reactor establishing open communication with said reactor for continuously receiving particulate polymer solids gravitating from said reactor thereby producing a fraction concentrated in particulate solids; measuring means for sensing the quantity of particulate solids contained in said receiving means; means for varying the velocity of reactants within said loop reactor; means for varying said velocity in response to a signal from said measuring means so as to maintain a substantially constant residence time for polymer within said receiving zone and means for withdrawing polymer product from said receiving means.

19. The apparatus of claim 18 wherein said measuring means is a solids depth sensing device.

20. Apparatus comprising in combination a tubular closed reactor with smooth bends, said reactor being substantially free from internal obstructions; means for introducing olefin reactant, polymerization catalyst and liquid hydrocarbon diluent into said reactor; means for continuously moving the contents of said reactor therethrough at a velocity in the turbulent flow range; receiving means comprising a vertically disposed appendage on a horizontal leg of said reactor establishing open communication with said reactor for continuously receiving particulate polymer solids gravitating from said reactor thereby producing a fraction concentrated in particulate solids; cooling means for maintaining the temperature of the particulate solids within said receiving means below the softening point of the polymer; measuring means for sensing the quantity of particulate solids contained in said receiving means; means for varying the velocity of reactants within said reactor; means for varying said velocity in response to a signal from said measuring means so as to maintain a substantially constant residence time for polymer within said receiving zone and means for withdrawing polymer product from said receiving means.

The apparatus of claim 20 wherein said cooling means comprises the injection of a diluent into said receiving means and wherein said measuring means is a solids depth sensing device.

References (Jilted by the Examiner UNITED STATES PATENTS 2,330,118 9/1943 Frey 196-2 2,376,833 5/1945 Teter 208-l53 2,825,721 3/1958 Hogan et al 26088.l 2,885,389 5/1959 Schappert 26094.9 2,908,734 10/1959 Cottle 26094.9

FOREIGN PATENTS 550,088 10/1956 Belgium. 1,172,905 2/ 1959 France.

JOSEPH L. SCHOFER, Primary Examiner.

MARK LIEBMAN, JOSEPH LIBERMAN, W. SHORT,

Examiners.

Patent Citations
Cited PatentFiling datePublication dateApplicantTitle
US2285389 *Jul 9, 1940Jun 9, 1942Akron Standard Mold CoPress
US2330118 *Jan 3, 1941Sep 21, 1943Phillips Petroleum CoHydrocarbon conversion and polymerization
US2376833 *Feb 19, 1941May 22, 1945Sinclair Refining CoArt of cracking hydrocarbons
US2825721 *Mar 26, 1956Mar 4, 1958Phillips Petroleum CoPolymers and production thereof
US2908734 *Aug 25, 1955Oct 13, 1959Phillips Petroleum CoMethod of and apparatus for controlling catalytic processes
BE550088A * Title not available
FR1172905A * Title not available
Referenced by
Citing PatentFiling datePublication dateApplicantTitle
US3374211 *Jul 27, 1964Mar 19, 1968Phillips Petroleum CoSolids recovery from a flowing stream
US3451785 *Oct 15, 1965Jun 24, 1969Phillips Petroleum CoPressure relief system for pressure vessels
US3544540 *Nov 12, 1968Dec 1, 1970Phillips Petroleum CoTemperature control system
US3666736 *Mar 24, 1969May 30, 1972Phillips Petroleum CoLow density ethylene-butene copolymers
US4121029 *Dec 6, 1976Oct 17, 1978Phillips Petroleum CompanyPolyolefin reactor system
US4199546 *Mar 16, 1978Apr 22, 1980Chemplex CompanyManufacture and recovery of olefin polymer particles
US4258158 *Aug 1, 1978Mar 24, 1981Basf AktiengesellschaftManufacture of ethylene homopolymers and copolymers
US4395523 *May 27, 1982Jul 26, 1983Chemplex CompanyMethod of making and recovering olefin polymer particles
US4448929 *Jun 1, 1982May 15, 1984Stauffer Chemical CompanyEncapsulation process
US4613484 *Nov 30, 1984Sep 23, 1986Phillips Petroleum CompanyLoop reactor settling leg system for separation of solid polymers and liquid diluent
US4794151 *Apr 8, 1987Dec 27, 1988Basf AktiengesellschaftBleeding to control concentration of monomer in cycle stream
US4801433 *Mar 20, 1986Jan 31, 1989Hitachi, Ltd.High viscosity liquids
US5143881 *Mar 11, 1991Sep 1, 1992Ulrich BueschgesTransition-metal catalyst component for a ziegler catalyst system, and the use of said system
US5143882 *Mar 11, 1991Sep 1, 1992Basf AktiengesellschaftTransition-metal catalyst component for a ziegler catalyst system, and the use of said system
US5164353 *Nov 14, 1989Nov 17, 1992Basf AktiengesellschaftSupported chromium oxide catalyst
US5188998 *Mar 19, 1991Feb 23, 1993Basf AktiengesellschaftOf an inorganic oxide support, a vanadium trihalide/alcohol complex, an organoaluminum catalyst component and an organic carboxylate
US5391654 *Dec 18, 1991Feb 21, 1995Neste OyMethod for homo- or copolymerizing ethene
US5756607 *Dec 13, 1994May 26, 1998Basf AktiengesellschaftPreparation of polymers of ethylene by suspension polymerization
US5977251 *Apr 1, 1997Nov 2, 1999The Dow Chemical CompanyNon-adiabatic olefin solution polymerization
US6214944Feb 2, 1999Apr 10, 2001Fina Technology, Inc.Polymerizing propylene including a propylene pressurization vessel operated under supercritical conditions
US6239235Jul 15, 1997May 29, 2001Phillips Petroleum CompanyMonomer, diluent and catalyst are circulated in a continuous loop reactor and product slurry is recovered by means of a continuous product take off.
US6326444Feb 19, 1997Dec 4, 2001Basell Polyolefin GmbhPreparation of polymers of alkenes by suspension polymerization
US6455010Jan 31, 2001Sep 24, 2002Fina Technology, Inc.Combined use of internal cooling of the pressurization vessel and a differential pressure cell to control the level of dense subcooled liquid propylene in the vessel; propylene is present above and below critical temperature and pressure
US6566460Aug 4, 2000May 20, 2003Equistar Chemicals, LpContinuous recovery of polymer from a slurry loop reactor
US6670431Feb 27, 2003Dec 30, 2003Exxonmobil Chemical Patents, Inc.Separating polymer solids from a liquid medium, drying the polymer, and recovering the inert diluent; flashing, condensation
US6730753Aug 28, 2001May 4, 2004Basell Polyolefine GmbhCatalyst systems of the ziegler-natta type and a process for preparing them
US6743869Jun 20, 2002Jun 1, 2004Phillips Petroleum CompanyPolymerizing, in a loop reaction zone, olefin monomer and olefin comonomer different from said monomer in a liquid diluent to produce a fluid slurry comprising liquid diluent and solid olefin polymer particles; maintaining; withdrawing
US6800698Mar 11, 2003Oct 5, 2004Exxonmobil Chemical Patents, Inc.Continuously separating polymer solids from liquid medium, drying polymer, and recovering diluent and unreacted monomers with reduction in compression needed for diluent vapor condensation to liquid diluent for reuse in process
US6806324Jun 20, 2002Oct 19, 2004Phillips Petroleum CompanyHigh solids slurry polymerization using heat exchange to condense the flashed diluent
US6833415Feb 19, 2002Dec 21, 2004Exxonmobil Chemical Patents, Inc.Continuous slurry polymerization process and appparatus
US6858682Mar 11, 2003Feb 22, 2005Exxonmobil Chemical Patents, Inc.For continuously separating polymer solids from a liquid medium comprising an inert diluent and unreacted monomers in slurry polymerization
US6884867 *Feb 19, 2003Apr 26, 2005Norchem IndustriesPrecondition for inverting, mixing, and activating polymers
US6911516Aug 1, 2000Jun 28, 2005Basell Polyolefine GmbhEthylene-C3-C12 alpha -olefin have a polydispersity Mw/Mn of <== 10, a density of from 0.85 to 0.95 g/cm3, a proportion of from 1 to 40% by weight of comonomer and a molar mass Mn above 150,000 g/mol
US6924248Jun 13, 2001Aug 2, 2005Basell Polyolefine GmbhCalcined hydrotalcite support, organic transition metal compound, especially a metallocene, optionally a cation-forming compound (e.g., an alumoxane), and at least one organic magnesium compound.
US6926868Nov 6, 2001Aug 9, 2005Exxonmobil Chemical Patents Inc.Separation polymer slurries; slurry loop; discharging conduit
US7019089Jun 28, 2001Mar 28, 2006Basell Polyolefine GmbhNovel supported, titanized chromium catalysts can be used for the homopolymerization of ethylene and the copolymerization of ethylene with alpha -olefins.
US7034090Feb 14, 2002Apr 25, 2006Exxonmobil Chemical Patents Inc.Continuous slurry polymerization volatile removal
US7202373Aug 18, 2003Apr 10, 2007Basell Polyolefine GmbhMonocyclopentadienyl complexes
US7268194Feb 28, 2002Sep 11, 2007Exxonmobil Chemical Patents Inc.Continuous slurry polymerization process and apparatus
US7348384Jan 12, 2006Mar 25, 2008Basell Polyolefine GmbhSupported, titanized chromium catalyst and its use for preparing homopolymers and copolymers of ethylene
US7507688Dec 5, 2003Mar 24, 2009Basell Polyolefine GmbhMonocyclopentadienyl complexes
US7507782May 19, 2004Mar 24, 2009Basell Polyolefine GmbhTransition-metal complexes with tridentate, nitrogen-containing ligands
US7534847Dec 18, 2003May 19, 2009Basell Polyolefine GmbhCopolymers of ethylene with α-olefins
US7541473Dec 18, 2003Jun 2, 2009Basell Polyolefine GmbhMonocyclopentadienyl complexes
US7541481Aug 11, 2003Jun 2, 2009Basell Polyolefin Gmbhpolymerization catalyst for the polymerization of olefins; molecular weight control of polyethylene, ethylene-hexene copolymer
US7544826Dec 14, 2004Jun 9, 2009Basell Polyolefine GmbhMonocyclopentadienyl complexes
US7572866Nov 22, 2005Aug 11, 2009Ineos Manufacturing Belgium NvUsing loop reactor; polymerizing olefin monomer with polymerization catalyst and diluent
US7575724Aug 1, 2007Aug 18, 2009Exxonmobil Chemical Patents Inc.Pressure flash tanks; pressure seal; discharging valve; continuous separation solid polymers
US7619090Sep 10, 2002Nov 17, 2009Basell Polyolefine GmbhPolymerization catalyst for polymerization of alpha-olefins
US7629464Dec 15, 2004Dec 8, 2009Basell Polyolefine Gmbhpolymerization catalyst for the polymerization of olefins; molecular weight control of polyethylene, ethylene-hexene copolymer; addition polymerization; 1-(diisopropyl(2-oxypyridine)silyl)-3-methylcyclopentadienyl)chromium dichloride
US7632899Nov 22, 2005Dec 15, 2009Ineos Manufacturing Belgium NvSlurry phase polymerisation process
US7671148Apr 21, 2005Mar 2, 2010Basell Polyolefine GmbhMixing organic transition metal compounds, hydrolyzed organoaluminum compound, and solvent, then impregnating dry porous support
US7683146Apr 23, 2007Mar 23, 2010Basell Polyolefine GmbhReacting an alkyl metal with a metallocene catalyst for the polymerization ofpropylene without formation of agglomerates or deposits in the reactor;minimize the influence of fluctuations of catalyst properties; efficiency; films; industrial scale
US7705097Jun 9, 2005Apr 27, 2010Basell Polyolefine Gmbhpreparing a homogenous solution of an organic or inorganic Cr compound (Cr/NO3/3) and Zr compound ( Zr(IV) propoxide) in an organic solvent (n-propanol), bringing solution in contact with a support to form catalyst precursor, calcining the precursor to form supported Cr2O3-ZrO2 catalyst
US7714091Jun 9, 2005May 11, 2010Basell Polyolefine GmbhCatalyst comprising chromium and zirconium for the polymerization and/or copolymerization of olefins
US7723448Oct 10, 2006May 25, 2010Basell Polyolefine Gmbhtwo different transition metal coordination compounds supported on an adduct containing magnesium chloride and an organoaluminum compound; polymerization catalyst for preparing polyethylene; control the morphology of the obtained polymer and to avoid fouling in the reactor
US7736597 *Mar 20, 2006Jun 15, 2010Chevron Phillips Chemical Company LpPumping apparatus and process for polymerization in loop reactors
US7767613Apr 25, 2005Aug 3, 2010Basell Polyolefine GmbhPolyethylene and catalyst composition for its preparation
US7776980Mar 18, 2006Aug 17, 2010Basell Polyolefine Gmbhpolymerization catalyst for the polymerization of olefins; molecular weight control of polyethylene, ethylene-hexene copolymer; preparation of dichloro(3-cyclopentadienyl-3-methyl-1-phenylbutylidene-N-2,6-diisopropylphenylamino)chromium(III)
US7781546Nov 22, 2005Aug 24, 2010Ineos Manufacturing Belgium NvSlurry phase polymerisation process
US7790119Mar 20, 2009Sep 7, 2010Ineos Manufacturing Belgium Nvloop reactor; olefin monomer optionally with an olefin comonomer in the presence of a polymerization catalyst in a diluent; the Froude number is maintained at or below 20; heat transfer coefficient stability and pump power stability
US7795167Aug 16, 2005Sep 14, 2010Basell Polyolefine GmbhCyclopentadienyl complexes of group 6 substituted by silyl halides
US7803736Dec 9, 2003Sep 28, 2010Basell Polyolefine Gmbhbringing support material into contact with protic medium having a water content less than 20% by weight and comprising a titanium compound and a chromium compound, wherein the protic medium comprises an alcohol, removing the solvent, optionally calcining
US7820116Jun 10, 2009Oct 26, 2010Ineos Manufacturing Belgium NvSlurry phase polymerisation process
US7834112Sep 10, 2002Nov 16, 2010Basell Polyolefine GmbhMethod of polymerization of olefins
US7838607May 4, 2007Nov 23, 2010Basell Polyolefine GmbhAntistatic for olefin polymerization and process for preparing it
US7902307 *Jan 20, 2010Mar 8, 2011Total Petrochemicals Research FeluyOlefin polymerization process with optimized product discharge
US7928051Apr 25, 2005Apr 19, 2011Basell Polyolefine GmbhPolyethylene for injection moldings
US7973114Oct 31, 2007Jul 5, 2011Basell Polyolefine GmbhMonocyclopentadienyl complexes
US8003740Jul 13, 2006Aug 23, 2011Basell Polyolefine GmbhMethod of controlling the relative activity of the different active centers of hybrid catalysts
US8008403Apr 25, 2005Aug 30, 2011Basell Polyolefine GmbhPolyethylene and catalyst composition for its preparation
US8022124Jan 24, 2007Sep 20, 2011Basell Polyolefine GmbhProcess for preparation of ethylene polymers for blown films
US8039569Apr 15, 2006Oct 18, 2011Basell Polyolefine GmbhPolyethylene molding compositions for injection molding applications
US8101692Mar 20, 2009Jan 24, 2012Ineos Manufacturing Belgium NvSlurry phase polymerisation process
US8133832Jul 22, 2008Mar 13, 2012Basell Polyolefine GmbhCatalyst system for polymerization of olefinic monomers, process for preparing polymers, and polymers prepared by the process
US8222356Jul 21, 2011Jul 17, 2012Basell Polyolefine GmbhProcess for preparing ethylene copolymers
US8227557Mar 1, 2008Jul 24, 2012Basell Polyolefine GmbhIron complexes and their use in polymerization processes
US8247587Dec 11, 2008Aug 21, 2012Basell Polyolefine GmbhMono-hydroindacenyl complexes
US8252875Jan 8, 2007Aug 28, 2012Basell Polyolefine GmbhProcess for the preparation of unsymmetric bis(imino) compounds
US8354063Apr 30, 2010Jan 15, 2013Chevron Phillips Chemical Company LpPumping apparatus and process for polymerization in loop reactors
US8409681Feb 22, 2010Apr 2, 2013Borealis AgMulti-stage process for producing multi-modal linear low density polyethylene
US8461266Oct 12, 2009Jun 11, 2013Borealis AgCable and polymer composition comprising a multimodal ethylene copolymer
US8471050Jul 20, 2010Jun 25, 2013Basell Polyolefine GmbhOrganometallic transition metal compound, catalyst system and preparation of polyolefins
US8501881Nov 11, 2010Aug 6, 2013Borealis AgProcess for olefin polymerization
US8501884Mar 31, 2008Aug 6, 2013Basell Polyolefine GmbhPolyethylene and catalyst composition and process for the preparation thereof
US8536289Dec 17, 2010Sep 17, 2013Basell Polyolefine GmbhProcess for the production of polyolefin films
US8546499Apr 26, 2010Oct 1, 2013Borealis AgLinear low density polyethylene with uniform or reversed comonomer composition distribution
US8563674May 27, 2010Oct 22, 2013Basell Polyolefine GmbhPolyethylene and catalyst composition for its preparation
US8580202 *Jun 30, 2010Nov 12, 2013Ineos Manufacturing Belgium NvSlurry phase polymerisation process
US8633125Jul 21, 2011Jan 21, 2014Basell Polyolefine GmbhCatalyst composition for preparation of polyethylene
US8664140Dec 12, 2009Mar 4, 2014Basell Polyolefine GmbhCatalyst system for olefin polymerization, its production and use
US8722832Nov 27, 2008May 13, 2014Basell Polyolefine GmbhEthylene terpolymers
US8722833Dec 18, 2007May 13, 2014Basell Polyolefine GmbhMultimodal polyethylene composition, mixed catalyst and process for preparing the composition
US8802781Jan 4, 2010Aug 12, 2014Basell Poliolefine Italia S.R.L.Polymer composition
US8822602Nov 8, 2011Sep 2, 2014Borealis AgHeterophasic propylene copolymers with stiffness/impact/flowability balance
US20130131288 *Jul 29, 2011May 23, 2013Total Research & Technology FeluyMethod for producing polyethylene
CN100431681CFeb 8, 2005Nov 12, 2008托塔尔石油化学产品研究弗吕公司Olefin polymerization process with optimized product discharge
DE102007017903A1Apr 13, 2007Oct 16, 2008Basell Polyolefine GmbhPolyethylen und Katalysatorzusammensetzung und Verfahren zu dessen Herstellung
EP1563898A1 *Feb 13, 2004Aug 17, 2005Total Petrochemicals Research FeluyOlefin polymerization process with optimized product discharge
EP2033975A1Apr 15, 2006Mar 11, 2009Basell Polyolefine GmbHCatalyst composition
EP2110173A1Apr 16, 2008Oct 21, 2009INEOS Manufacturing Belgium NVPolymer stream transfer
EP2130859A1Jun 2, 2008Dec 9, 2009Borealis AGPolymer compositions having improved homogeneity and odour, a method for making them and pipes made thereof
EP2130862A1Jun 2, 2008Dec 9, 2009Borealis AGPolymer compositions and pressure-resistant pipes made thereof
EP2130863A1Jun 2, 2008Dec 9, 2009Borealis AGHigh density polymer compositions, a method for their preparation and pressure-resistant pipes made therefrom
EP2156884A2May 18, 2007Feb 24, 2010INEOS Manufacturing Belgium NVPolymerisation process
EP2156885A2May 18, 2007Feb 24, 2010INEOS Manufacturing Belgium NVPolymerisation process
EP2156886A2May 18, 2007Feb 24, 2010INEOS Manufacturing Belgium NVSlurry phase polymerisation process
EP2168676A1Nov 22, 2005Mar 31, 2010INEOS Manufacturing Belgium NVSlurry phase polymerisation process
EP2177542A1Nov 22, 2005Apr 21, 2010INEOS Manufacturing Belgium NVSlurry phase polymerisation process
EP2182524A1Oct 31, 2008May 5, 2010Borealis AGCable and Polymer composition comprising a multimodal ethylene copolymer
EP2182525A1Oct 31, 2008May 5, 2010Borealis AGCable and polymer composition comprising a multimodal ethylene copolymer
EP2182526A1Oct 31, 2008May 5, 2010Borealis AGCable and polymer composition comprising an multimodal ethylene copolymer
EP2186833A1Nov 17, 2008May 19, 2010Borealis AGMulti-stage process for producing polytheylene with lowered gel formation
EP2223943A1Feb 25, 2009Sep 1, 2010Borealis AGMultimodal polymer of propylene, composition containing the same and a process for manufacturing the same
EP2223944A1Feb 26, 2009Sep 1, 2010Borealis AGProcess for producing semicrystalline propylene polymers
EP2228394A1Feb 24, 2009Sep 15, 2010Borealis AGMulti-stage process for producing multi-modal linear low density polyethylene
EP2228395A1Feb 24, 2009Sep 15, 2010Borealis AGImproved multi-stage process for producing multi-modal ethylene polymer composition
EP2236577A2Feb 18, 2009Oct 6, 2010Basell Polyolefine GmbHPolyethylene composition
EP2246368A1Apr 30, 2009Nov 3, 2010Borealis AGImproved ethylene polymerization catalyst composition
EP2246369A1Apr 30, 2009Nov 3, 2010Borealis AGLinear low density polyethylene with uniform or reversed comonomer composition distribution
EP2246372A1Apr 30, 2009Nov 3, 2010Borealis AGImproved multi-stage process for producing multi-modal linear low density polyethylene
EP2256158A1May 26, 2009Dec 1, 2010Borealis AGPolymer composition for crosslinked articles
EP2256159A1May 26, 2009Dec 1, 2010Borealis AGPolymer composition for crosslinked pipes
EP2277621A2Nov 22, 2005Jan 26, 2011INEOS Manufacturing Belgium NVSlurry phase polymerisation process
EP2277921A1Nov 22, 2005Jan 26, 2011INEOS Manufacturing Belgium NVSlurry phase polymerisation process
EP2316863A1Oct 30, 2009May 4, 2011INEOS Manufacturing Belgium NVSlurry phase polymerisation process
EP2322565A2Apr 25, 2005May 18, 2011Basell Polyolefine GmbHCatalyst composition for the preparation of polyethylene
EP2322568A1Nov 13, 2009May 18, 2011Borealis AGProcess for producing an olefin polymerization catalyst
EP2374823A1Apr 7, 2010Oct 12, 2011Borealis AGProduction of alpha-olefin copolymers in a loop reactor with variable comonomer feed
EP2383298A1Apr 30, 2010Nov 2, 2011Ineos Europe LimitedPolymerization process
EP2383301A1Apr 30, 2010Nov 2, 2011Ineos Europe LimitedPolymerization process
EP2397221A1Jun 17, 2010Dec 21, 2011Borealis AGControl system for a gas phase reactor, a gas phase reactor for catalytic production of polyolefines, a method for catalytic productions of polyolefines and a use of the control system
EP2399943A1Jun 28, 2010Dec 28, 2011Borealis AGProcess for producing polyethylene
EP2428526A1Sep 13, 2010Mar 14, 2012Borealis AGProcess for producing polyethylene with improved homogeneity
EP2452957A1Nov 12, 2010May 16, 2012Borealis AGImproved process for producing heterophasic propylene copolymers
EP2452959A1Nov 12, 2010May 16, 2012Borealis AGProcess for producing propylene random copolymers and their use
EP2452960A1Nov 12, 2010May 16, 2012Borealis AGProcess for preparing propylene polymers with an ultra high melt flow rate
EP2452976A1Nov 12, 2010May 16, 2012Borealis AGHeterophasic propylene copolymers with improved stiffness/impact/flowability balance
EP2535372A1Jun 15, 2011Dec 19, 2012Borealis AGIn-situ reactor blend of a Ziegler-Natta catalysed, nucleated polypropylene and a metallocene catalysed polypropylene
EP2570455A1Sep 16, 2011Mar 20, 2013Borealis AGPolyethylene composition with broad molecular weight distribution and improved homogeneity
EP2599828A1Dec 1, 2011Jun 5, 2013Borealis AGMultimodal polyethylene composition for the production of pipes with improved slow crack growth resistance
EP2607391A1Dec 21, 2011Jun 26, 2013Basell Polyolefine GmbHProcess for controlling the polymer composition of an ethylene copolymer obtained by a catalyst system comprising a transition metal catalyst component and a Ziegler catalyst component
EP2617741A1Jan 18, 2012Jul 24, 2013Borealis AGProcess for polymerizing olefin polymers in the presence of a catalyst system and a method of controlling the process
EP2727958A1Nov 8, 2011May 7, 2014Borealis AGHeterophasic propylene copolymers with improved stiffness/impact/flowability balance
EP2730611A1Nov 9, 2012May 14, 2014Abu Dhabi Polymers Company Limited (Borouge)Drip Irrigation pipe comprising a polymer composition comprising a multimodal polyethylene base resin
EP2730612A1Nov 9, 2012May 14, 2014Abu Dhabi Polymers Company Limited (Borouge)Polymer composition comprising a blend of a multimodal polyethylene and a further ethylene polymer suitable for the production of a drip irrigation pipe
EP2740748A1Dec 7, 2012Jun 11, 2014Borealis AGMethod of polymerizing olefins in slurry reactors
EP2740761A1Dec 5, 2012Jun 11, 2014Borealis AGPolyethylene composition with improved balance of slow crack growth resistance, impact performance and pipe pressure resistance for pipe applications
EP2743000A1Dec 13, 2012Jun 18, 2014Basell Poliolefine Italia S.r.l.Catalyst system for the preparation of polyolefins
EP2743278A1Dec 11, 2012Jun 18, 2014Basell Polyolefine GmbHProcess for degassing and buffering polyolefin particles obtained by olefin polymerization
WO1992012181A1 *Dec 18, 1991Jul 23, 1992Neste OyA method for homo- or copolymerizing ethene
WO1997036942A1 *Apr 1, 1997Oct 9, 1997Gary A CampOlefin solution polymerization
WO2003074167A1 *Feb 28, 2002Sep 12, 2003Exxonmobil Chem Patents IncContinuous slurry polymerization process in a loop reactor
WO2005079967A1 *Feb 8, 2005Sep 1, 2005Andre LewalleOlefin polymerization process with optimized product discharge
WO2005123793A1Jun 9, 2005Dec 29, 2005Basell Polyolefine GmbhCatalyst comprising chromium and zirconium for the polymerization and/or copolymerization of olefins
WO2006056756A1 *Nov 22, 2005Jun 1, 2006Innovene Mfg Belgium NvSlurry phase polymerisation process
WO2007060115A1Nov 14, 2006May 31, 2007Basell Polyolefine GmbhPolyethylene composition suitable for the preparation of films and process for preparing the same
WO2009103516A2Feb 18, 2009Aug 27, 2009Basell Polyolefine GmbhAdhesive polymer composition
WO2010069527A1Dec 12, 2009Jun 24, 2010Basell Polyolefine GmbhCatalyst system for olefin polymerization, its production and use
WO2010081676A1Jan 13, 2010Jul 22, 2010Basell Polyolefine GmbhPolyethylene copolymers
WO2010081753A1Jan 4, 2010Jul 22, 2010Basell Poliolefine Italia S.R.L.Polymer composition
WO2010097351A1Feb 22, 2010Sep 2, 2010Borealis AgMulti-stage process for producing multi-modal linear low density polyethylene
WO2010097352A1Feb 22, 2010Sep 2, 2010Borealis AgImproved multi-stage process for producing multi-modal ethylene polymer composition
WO2010097409A1Feb 24, 2010Sep 2, 2010Borealis AgMultimodal polymer of propylene, composition containing the same and a process for manufacturing the same
WO2010136373A1May 20, 2010Dec 2, 2010Borealis AgPolymer composition for crosslinked pipes
WO2010136374A1May 20, 2010Dec 2, 2010Borealis AgPolymer composition for crosslinked articles
WO2011012245A1Jul 20, 2010Feb 3, 2011Basell Polyolefine GmbhOrganometallic transition metal compound, catalyst system and preparation of polyolefins
WO2011023532A1Aug 10, 2010Mar 3, 2011Borealis AgImproved ethylene polymerization catalyst composition
WO2011051367A1Oct 28, 2010May 5, 2011Ineos Manufacturing Belgium NvSlurry phase polymerisation process
WO2011058088A1Nov 11, 2010May 19, 2011Borealis AgProcess for recovering a transition metal compound
WO2011058089A1Nov 11, 2010May 19, 2011Borealis AgProcess for producing a polymerization catalyst
WO2011058091A1Nov 11, 2010May 19, 2011Borealis AgProcess for olefin polymerization
WO2011072850A1Dec 16, 2010Jun 23, 2011Basell Polyolefine GmbhPolymerization process in the presence of an antistatic agent
WO2011085937A1Dec 24, 2010Jul 21, 2011Ineos Europe LimitedPolymer powder storage and/or transport and/or degassing vessels
WO2011085951A1Jan 8, 2011Jul 21, 2011Basell Polyolefine GmbhOligomerization of olefins
WO2011134797A1Apr 13, 2011Nov 3, 2011Ineos Commercial Services Uk LimitedPolymerization process
WO2011134798A1Apr 13, 2011Nov 3, 2011Ineos Commercial Services Uk LimitedPolymerization process
WO2011147573A2May 26, 2011Dec 1, 2011Basell Polyolefine GmbhProcess for preparing a supported catalyst system for olefin polymerization, the catalyst system and its use
WO2011160828A1Jun 22, 2011Dec 29, 2011Basell Polyolefine GmbhProcess for the production of high-strength polyolefin compositions and polyolefin compositions produced by this process
WO2012034869A1Sep 1, 2011Mar 22, 2012Borealis AgProcess for producing polyethylene with improved homogeneity
WO2012055943A2Oct 27, 2011May 3, 2012Basell Polyolefine GmbhOligomerization of olefins
WO2012062733A1Nov 8, 2011May 18, 2012Borealis AgProcess for producing propylene random copolymers and their use
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WO2013156491A1Apr 16, 2013Oct 24, 2013Ineos Europe AgCatalyst for the polymerisation of olefins, process for its production and use
WO2014086648A1Nov 28, 2013Jun 12, 2014Borealis AgMethod of polymerizing olefins in slurry reactors
Classifications
U.S. Classification526/64, 422/132, 159/4.1, 159/48.1, 528/503, 159/DIG.100, 528/498
International ClassificationC08F10/00, B01J19/18, B01J10/00, B62M7/00
Cooperative ClassificationC08F10/00, B62M2701/0015, B62M7/00, B01J2219/00094, B01J19/1837, Y10S159/10
European ClassificationB62M7/00, C08F10/00, B01J19/18C8